Manufacture of secondary aliphatic monoketomonosulphonates



Patented Jan. 19, 1943 MANUFACTURE OF SECONDARY ALIPHATIC MONOKETOMONOSULPHONATES James H. Werntz, Brandywine Hundred, Del., as-

signor to E. I. du Pont de Nemours & Company,

UNITED STATES PATENT OFFICE which have surface active properties.

Wilmington, Del., a corporation of Delaware No Drawing, Application April 23,1940, Serial No. 331,164

6 Claims. 260-513) This invention relates to new surface active compounds, their methods of production, and their uses. More particularly this invention relates to the production and utilization of new secondary aliphatic monoketomonosulphonates in which atleast 12 carbon atoms are in a" these new compounds in various connections wherein surface active compounds are commonly employed. Other objects will appear hereinafter.

These objects are accomplished by the following invention according to which new secondary aliphatic monoketomonosulphonates which contain at least 12 carbon atoms in a straight chain and have the general formula R-(SO;X)-(CA'H),COR' in which R represents an aliphatic hydrocarbon radical containing at least 4 carbon atoms, A is amember of the class consisting of hydrogen and aliphatic hydrocarbon radicals containing less than 4 carbon atoms, X stands for a cation, A is a member of the class consisting of hydrogen and aliphatic hydrocarbon radicals containing less than 4 carbon atoms, 1 stands for one of the numbers 0 and 1, and R represents an aliphatic radical containing at least 4 carbon atoms are prepared by reacting a solution of a bisulphite with alpha unsaturated aliphatic ketones which contain at least 12' carbon atoms in a straight chain and have the general formula A A R-C=C-COR in which R represents an aliphatic hydrocarbon radical containing at least 4. carbon atoms, A and A are members of the class consisting of hydrogen and aliphatic hydrocarbon radicals containing less than 4 carbon atoms, and R represents an aliphatic radical containing at least 4 carbon atoms. In most instances it seems that in the major portion of the product the sulphonate group is attached to the carbon atom which is beta to the keto group. Accordingly, the principal products obtained accord ng to this invention appear to correspond to the general formula given above when y=1.

In accordance with thepreferred embodiments of this invention new secondary aliphatic monoketomonosulphonates which contain at least 12 carbon atoms in a straight chain and have the general formula in which-R represents an aliphatic hydrocarbon radical containing at least 4 carbon atoms, X stands for a cation, 1,! stands for one of the numhere 0 and 1, and R represents an aliphatic hydrocarbon radical containing at least -4 carbon atoms are prepared by reacting a solution of a bisulphite with alpha unsaturatedaliphatic ketones which contain at least 12 carbon atoms in a straight chain and'have the general formula H H R-O=OOO--R' inwhich R represents an aliphatic hydrocarbon radical containing at least 4 carbon atoms, and

R stands for an aliphatic hydrocarbon radical containing at least 4 carbon atoms. The reaction between the bisulphite and these alpha unsaturated aliphatic ketones is preferably carried out at elevated temperatures and under superatmospheric pressures.

The following examples illustrate but do not limit the invention. All parts are given by weight.

EXAMPLE I v Sodium-6(5,11-diethylpentadecen-9-one-8) sulphonate A reaction mixture comprising 14 parts of 5,11-diethylpentadecadiene-G,9-one-8 (preparedby reacting 2-ethylhexaldehyde with acetone), 39 parts of ethyl alcohol, 5.7 parts of sodium bisulphite and 50 parts of waterwas heated 24 hours at C. in a rotating nickel bomb. The resulting solution was filtered and evaporated on the steam bath, and the product was purified by extracting with ethyl ether. Upon evaporation of the ether a brown oil was obtained which dissolved in water to give a foaming solution that wet powdered sulphur very rapidly. Dilute aqueous solutions of this product, which is be-: lieved to be sodium-6(5,11-diethylpentadecen-9- one-8) sulphonate, wet cotton 'skeins readily when tested by the method of Draves and Clarkson (American Dyestufi's Reporter 20, 201 931) i.

Exmui II Sodium-3(Z-methzrlhexadecanone-S) sulphonate A reaction mixture comprising 12.6 parts of 2-methylhexadecen-3-one-5 (prepared by reacting methyl undecyl ketone with isobutyraldehyde) 39 parts of ethyl alcohol, 6 parts of sodium bisulphite and 50 parts of waterwere heated 17 The resulting clear solution was evaporated on the steam bath and a soap-like material was obtained. The product which contained sodium- 3(2-methylhexadecanone-5) sulphonate was purified by extraction in a Soxhlet extractor with anhydrous ethyl ether. Evaporation of the ether solution yielded a viscous-syrup. Aqueous solutions of this product foamed, wet powdered sulphur, and were good wetting agents when tested by the method of Draves-and Clarkson.

EXAMPLE. III Sodium-7 (pentadecanone-9) sulphonate hour at 150 C. in a rotating monel metal bomb. 7

A reaction mixture comprising 11.2 parts of pentadecen-7-one-9 (prepared by condensing heptaldehyde with methyl hexyl ketone), 39 parts of ethyl alcohol, 6 parts of sodium bisuiphite and 50 parts of water was heated 18 hours at 150 C. in a rotating nickel bomb. The resulting clear solution was diluted with an additional 50 parts of water and extracted four times with ethyl ether. The ether solution was then saturated with sodium chloride and separated from a water layer. Evaporation of the ether layer left a soft, yellow gum which sulphur analysis indicated to be a hydrated sodium- !(pentadecanone-Q) sulphonate. Dilute aqueous solutions of this material foamed and wet powdered sulphur' and were good wetting agents when tested by the method of Graves and Clarkson.

EXAMPLE IV Sodium-6 (S-ethyltetradecanone-il) sulphonate ExA'MPnri V Sodium-7 (i-methylpentadecanone-9) sulphonate A reaction mixture comprising 10 parts of 'Lmethylpentadecen-I-one-9 (prepared by treating methyl hexyl ketone with zinc chloride), 39 parts of ethyl alcohol, 5.2 parts of sodium bisulphite, and 50 parts of water was heated 18 hours at 150 C. in a rotating nickel bomb. The reaction product was extracted three times with ethyl ether, and the extract diluted with water and evaporated on the steam bath to remove the alcohol and ether. The resulting aqueous solution was separated from an oil layerand was evaporated on the steam bath. The product was flnally dried over phosphorus pentoxide in a vacuum desiccator. A colorless oil was obtained which sulphur analysis indicated to be a hydrated sodium-7 (7-methylpentadecanone-9) sulphonate. Dilute aqueous solutions wet powdered sulphur and were good wetting agents when tested by the method of Draves and Clarkson.

Exsmui VI Sodium-9 (5,8-diethyl-6-hz dr0zydodecene-4- one-7) sulphonate A reaction mixture comprising 12.6 parts of 5,8 diethyl 6 hydroxydodecadiene 4,8 -one-"l (prepared by condensing 2-ethylhexenal with itself in the presence of sodium cyanide), 39 parts of ethyl alcohol, 6.3 parts of sodium.bisulphite, and parts of water was heated 21 hours at 150 C. 'in a stainless steel rotating bomb. The reaction product was heated on the steam bath to drive off the alcohol and a waterinsoluble brown oil separated. The water layer was evaporated to dryness on the steam bath and extracted with hot ethyl alcohol. The alcohol-extractable portion was next evaporated to dryness and dried over phosphorus pentoxide at 2 mm. The resulting brown gum was considered to be sodium-9 (5,8-diethyl-6-hydroxydodecen-4-one-7) sulphonate.

EXAMPLE VII Sodium-8 (3,9-diethyl tridecanone-B) sulphonate A reaction mixture comprising 15.1 parts of 3,9-diethyltridecen-7-one-6 (obtained by condensing Z-ethylhexaldehyde with 3-ethylheptanone-6), 39 parts of'ethyl alcohol, 7.3 parts of sodium bisulphite, and 50 parts of water was heated 18 hours at C. in a rotating Monel metal bomb. The reaction product was diluted with an additional 50 parts of water and extracted four times with ethyl ether. The ether extracts were treated with potassium carbonate to remove the water, and the ether and alcohol then evaporated. The resulting oily product was then redissolved in ether, dried with potassium carbonate, filtered, and the ether evaporated. The resulting clear, yellow oil was considered to be sodium-8 (3,9-diethyl tridecanone-G) sulphonate containing some water. It was readily soluble in ethanol and in petroleum ether, and dilute aqueous solutions wet cotton skeins very rapidly when tested by the method of Draves and Clarkson. As a wetting agent, this product was superior for wetting cotton to the products described in preceding Examples I' VI, inclusive.

Any water-soluble bisulphite or compound capable of yielding bisulphite ions (HSOs) may be employed in the reaction. While I have usually used sodium bisulphite, I may also employ ammonium bisulphite, aniline bisulphite, free sulphurous acid, dimethylamine bisulphite, methylamine bisulphite, dimethyl, aniline bisulphite, pyridine bisulphite, triethanolamine bisulphite, calcium bisulphite, potassium bisulphite, etc. Under certain conditions, sulphurous acid may be reacted jointly in the presence of a base, such as ammonia, methylamine, triethanolamine, etc., and the same effect is obtained as if a bisulphite were present. At normal temperatures ammonium bisulphite appears to react better than sodium bisulphite.

While any polar solvent or solvent which promotes formation of bisulphite ions may be used, water, methanol, methanol-water, ethanol-water and ethanol have proved to be excellent solvents for carrying out the reaction and are preferred. The type of solvent to be employed depends upon the temperature to be used and upon the remore soluble in methanol than in ethanol. Methanol and ethanol are preferred to dimethylformamide, ethyl ether, and dioxan as solvents because of the higher solubility of sodium bisulphite in the alcohols and the higher efliciency of the alcohols.

This invention contemplates the use of pro moter catalysts such as kieselguhr, kaolin, pulverized charcoal, gas carbon black, powdered silica gel, vermiculite, diatomaceous earth, fuller's earth, Japanese acid clay, bentonite, and natural silicates such as Indianaite.

This invention is especially useful in providing a direct route to water-soluble salts of aliphatic sulphonic acids. If desired, a water-soluble salt such as sodium, ammonium, etc. may be converted to and isolated as a less water-soluble salt, as, for example, thebarium or calcium salt. The free sulphonic acids are readily obtained by treating the barium or calcium sulphonates with sulphuric acid or ortho-phosphoric acid. The free sulphonic acids are also obtained by using in the process dilute aqueous solutions of sulphurous acid in place of water-soluble bisulphites. The free sulphonic acids may be converted by known I methods to esters or amides which are of interest as solvents, plasticizers, etc,

Suitable unsaturated aliphatic ketones for the preparation of the sulphonates of this invention are obtained in a number of ways. It is essential, however, in order to obtain products with valuable surface-active properties, that the intermediates be alpha unsaturated aliphatic ketones and that they contains, straight carbon chain of at least 12 carbon atoms. Suitable intermediates are readily obtained by condensing aldehydes with ketones. Less preferred methods are the condensation of alpha unsaturated aldehydes by a benzoin-type condensation, by the condensation of ketones with themselves or by reacting aldehydes with diketene.

Unsaturated ketones derived from aldehydes,

in other words, alpha unsaturated aliphatic ketones which contain at least 12 carbon atoms in a straight chain and have the general formula H H 'R,C=CCOR' in which R. and R represent aliphatic hydrocarbon radicals containing at least 4 carbon atoms are the preferred starting materials for reaction with sodium bisulphite.

A few examples of alpha unsaturated ketones suitable for use in this invention are 2-methylheptadecen--one-4,

C11H23CH=CHCOCH2CH (CH3) 2 prepared from lauraldehyde and methyl isobutyl ketone; 2-methyldodecen-5-one-4,

C6H13CH=CHCOCH2CH(CH3) 2 prepared from heptaldehyde and methyl isobutyl ketone; 2.8.12-trimethyltridecatrien-5,7,11-one-4, (CH3) 2C=CHCH2CH2C(CH3) CHCH=CHCOCH2CH(CH3) 2 prepared from citral and methyl isobutyl ketone; 2-methyl-8-ethyldodecen-3-one-5,

CHaCH( CH2) CH=CHCOCH2CH2CH(C2H5) C4110 prepared from 5-ethylnonanone-2 and isobutyraldehyde; 5-ethylhexadecen-9-one-8,

CcHmCH=CHCOCH2CH2CH(C2Hs) 04H: prepared from 3-ethylheptanone-6 and heptalde- 5 hyde: 3-ethyltetradecen-7-one-6.

CHaCHzCHiC-aHs) CHzCHzCOCH=CHCaH1a prepared from 3-ethylheptanone-6 and heptalehyde; 9-ethyltridecen-7-one-6, I C4HOCH(C2H5) CH=CHCOC5H11 10 prepared from z-ethylhexaldehyde and methyl amyl ketone; 3,9-diethyltridecen-4-one-6, CHaCHzCH(C2Hs) CH:

CHCOCHzCHzCH CzHs) C4He prepared from 5-ethylnonanone-2 and 2-ethylbutyraldehyde; 9-ethyltridecen-4-one-6,

C3H1CH=CHCOCH2CH2CH(CzHs) 04H prepared from 5-ethylnonanone-2 and butyraldehyde; 9-ethyltrideoadien-4,7-one-6,

C4H0CH(C2H5) CH=CHCOCH=CHC3H1 prepared from z-ethylhexaldehyde' and butylideneacetone; 6-propyl 8-ethyl-dodecen-6-one-5, C4H9CH(C2H5) CH=C(C1H1) COC4Ha prepared from 2-ethylhexaldehyde and dibutyl ketone; 9-ethylq5-methyltridecadlen-4,7-one-6, CsH'1CH=C(CHa) -COCH=CHCH(C2H5) 04H:

prepared from z-ethylhexaldehyde and 3- methylhepten-3-one-2; 9 ethyl 5 methyltridecen-l-one-G,

C4HoCH(CHa) COCH=-CHCH(C:H5) CiHD prepared from 3-methylheptanone-2 and 2- ethylhexaldehyde, etc.

The new compositions covered in this case belong to the class of surface-active or capillaryactive materials in that they have colloidal properties and may, therefore. be advantageously used in any process involving wetting, penetrating,

deterging, dispersing, emulsifying, frothing;

foaming and kindred phenomena. These compositions may be employed in pure or standard- 40 ized form and,.if desired, in conjunction with known processing or treating agents. They may be used by themselves or in combination with other surface-active agents in any relation in which surfaceactive agents having colloidal properties have heretofore been used.

This invention provides an economical route for the preparation of aliphatic monoketomonosulphonates which display unexpectedly high wetting efiiciency. The preparation of surfaceactive agents by the addition of a water-soluble salt of sulphurous acid to the olefinic bond of an alpha unsaturated aliphatic ketone has not previously been reported. In carrying out the reaction with the highmolecular weight ketones of this invention, it is preferred to employ elevated temperatures and 'to operate under pressure in order to obtain high yields of product in a reasonable length of time. It is believed that the high efilciency of the products of this invention is due in part to the close proximity of the keto to the sulphonate group. In general, it is considered that the sulphonate group is attached to the carbon atom beta to the keto group, but it may be in some cases that the sulphonate group is attached to the alpha carbon atom. In any case, the products of this invention contain one sulphonate group and one free ketone group.

The above description and examples are intended to be illustrative only and not to limit the scope of the invention. Any departure therefrom or variation thereof which conforms to the spirit of the invention and which is included within the scope of the appended claims is to be rearded as an embodiment of this invention.

in which R represents an aliphatic hydrocarbon radical containing at least 4 carbon atoms, and

.R' stands for an aliphatic hydrocarbon radical containing at least 4 carbon atoms.

2. A process of making a secondary aliphatic monoketomonosulphonate which contains at least 12 carbon atoms in a straight chain which comprises heating and agitating in a closed reaction vessel an ethanol-water solution containing sodium bisulphite and an alpha unsaturated aliphatic ketone which contains at least 12 carbon atoms in a straight chain and has the general formula in which R represents an aliphatic hydrocarbon .radical containing at least 4 carbon atoms. and

R stands for an aliphatic hydrocarbon radical containing at least 4 carbon atoms.

8. A process of making a secondary aliphatic monoketomonosulphonate which contains at least 12 carbon atoms in a straight chain which comprises agitating a solution of a bisulphite in a polar solvent with an alpha unsaturated aliphatic ketone which contains at least 12 carbon atoms in a straight chain and has the general formula in which R represents an aliphatic hydrocarbon radical containing at least 4 carbon atoms, A and A are members of the class consistingot hydrogen and aliphatic hydrocarbon radicals containing less than 4 carbon atoms, and R represents an aliphatic radical containing at least 4 carbon atoms.

4. A process of making sodium-6(5,11-diethylpentadecen-9-one-8) sulphonate which comprises heating and agitating an ethanol-water solution 1 containing 5,1l-diethylpentadecadiene-6,9-one-8 and sodium bisulphite.

5. A process of making sodium-7(pentadecanone-9) sulphonate which comprises heating and agitating an ethanol-water solution containing pentadecen-7-one-9 and sodium bisulphite.

6. A process of making sodium-8(3,9-diethyl tridecanone+6) sulphonate which comprises heating and agitating an ethanol-water solution containing 3,9-diethyltridecen-7-one-6 and sodium bisulphite. 1

JAlVlES H. WERNTZ.

CERTIFICATE OF CORRECTION. Patent No.- 2,5O8, 8l;.l. January 19, 1914.5.

JAMES H. 'WERN'IZ.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows Page 5, second column, line 74., for "5-ethylheptanone-6" rea d 5-ethy1nonanone-2--; line 7-8, for heptglehyde read --he1ta1dehyde--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this l th day of nay, A. 1;. 1915.

Henry Van Ar sdale, (Seal) 7 Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION. v Patent No. 2 08,81 1. January 19, 191g.

JAMES H. WERN'IZ.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, secand column, line 1 for "5-ethylheptanone-6" read --5-ethy1nonanone2--; line 7-8, for "heptalehyde" read "heptaldehyde and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

This Certificate supersedes Certificate of Correction issued May 11., 1%}.

. Signed and sealed this 1 th day of June, A. D. 1915.

Henry Van Areqale,' (Seal) Acting Commissioner of Patents. 

